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51.
Spectroscopic, chemical, thermal, and voltammetric analyses on six kinds of alkylcarboxylate-stabilized silver nanoparticles 4.7 nm in diameter were carried out with an aim to reveal the effect of alkylcarboxylates on the optical, thermal, geometric, and electrochemical properties of the nanoparticles. These nanoparticles are composed of silver atoms and silver alkylcarboxylates having even numbers, m, of carbon atoms from 8 to 18. As a measure of the structure of the nanoparticles, the ratio of the number of silver atoms (nAg) to that of alkylcarboxylates (ns) per nanoparticle was evaluated by means of titration through chemical oxidation, voltammetric currents, and thermal gravimetric analysis. It increased with an increase in m and ranged from 1.3 to 9.8. Properties of the nanoparticle have been exhibited in absorbance of the UV-vis spectra at the point of the proportionality to n(Ag), voltammetric currents of which values were close to the theoretical values at the diffusion of particle itself, and the m-independent kinetic energy of the thermal decomposition and the overpotential of the reduction. They are not observed for the composed species, that is, silver atoms and silver alkylcarboxylate molecules. 相似文献
52.
UVB irradiation of normal human skin favors the development of type-2 T-cells in vivo and in primary dermal cell cultures 总被引:1,自引:0,他引:1
Di Nuzzo S Sylva-Steenland RM Koomen CW Nakagawa S van Breemen M de Rie MA Das PK Bos JD Teunissen MB 《Photochemistry and photobiology》2002,76(3):301-309
To determine the effect of UVB exposure on the balance of type-1 or type-2 T-cells in skin, we examined the expression of key markers interferon (IFN)-gamma and interleukin (IL)-4 in cryostat sections. IFN-gamma mRNA was clearly detectable in nonirradiated control skin, and IFN-gamma protein was found in 2% of the dermal CD3pos T-cells, whereas IL-4 mRNA was hardly detectable, and no IL-4 protein was found. In contrast, IL-4 mRNA expression increased upon irradiation, and IL-4 was found in 2% of the T-cells at day 2 after UVB-exposure. Concomitantly, IFN-gamma mRNA expression decreased, and IFN-gamma protein became absent. We also analyzed T-cells present in primary dermal cell cultures, which were used as an in vitro equivalent of the in vivo situation. As compared with T-cells from control skin, T-cells in dermal cell cultures from UVB-exposed skin displayed an increased IL-4 and decreased IFN-gamma expression. No such skewing occurred when the T-cells from irradiated skin were cloned in the absence of a dermal microenvironment. Except for an occasional positive T-cell, type-1-associated cell-surface markers (CCR5, CXCR3) or type-2 markers (CCR3, CD30, CRTH2) were undetectable in situ. But these markers were expressed on cultured dermal T-cells from UVB-exposed and control skin at a comparable level, but did not correlate with the IFN-gamma and IL-4 production. Altogether, UVB-induced changes of the dermal microenvironment favor the development of type-2 T-cells. 相似文献
53.
Akio Kamimura Rie MoritaKenji Matsuura Hiromasa MitsuderaMasashi Shirai 《Tetrahedron》2003,59(50):9931-9938
A convenient stereoselective synthesis of β-lactams from thio-Michael/aldol tandem adduct is described. syn-Selective tandem reaction followed by amidation and intramolecular SN2 reaction provided β-lactams in diastereomerically pure form. The tandem reaction with aliphatic aldehydes, on the other hand, afforded a mixture of diastereomers of corresponding tandem adducts in about 3:1 ratio so that the conversion to β-lactams afforded a diastereomeric mixture. As an alternative approach to prepare the tandem adducts, the stereoselective Michael addition of aliphatic thiols to Baylis-Hillman adduct was developed. The stereoselectivity was sensitive to the protective group at the hydroxyl group and TBS protection brought the most successful syn-selective formation of the tandem adducts. The procedure could be applied to the ketone derivatives of the Baylis-Hillman adduct but no selectivity was observed for the nitrile-Baylis-Hillman adducts. A similar conversion of the adduct provided desired β-lactams stereoselectively. 相似文献
54.
Akira Matsumoto Yutaka Kukimoto Kazuhiro Aoki Masayoshi Oiwa 《Journal of polymer science. Part A, Polymer chemistry》1983,21(12):3493-3502
Seven glycol bis(allyl phthalate)s (GBAP) and four glycol bis(allyl succinate)s (GBASu) as reactive oligomers were prepared and their polymerization behaviors were investigated in detail in terms of cyclopolymerization and gelation as compared with diallyl dicarboxylates. Thus, the rates of polymerization of GBAPs were reduced compared to diallyl phthalate, being attributed to the steric effect on the intermolecular propagation of the uncyclized radical, whereas those of GBASus were enhanced as a consequence of intermolecular association by dipole–dipole interaction in polar GBASu monomers. Cyclization was enhanced in the following order: diallyl aliphatic dicarboxylates series < GBASu series < GBAP series. Gelation was discussed according to Gordon's theory; the actual gel-point conversions increased with an increase in the molecular weight of monomers, although the discrepancy between actual and theoretical gel-point conversion inversely tended to be decreased. The decreased delay in gelation with an increase of the molecular weight of monomers is ascribed to the reduction of excluded volume effects on crosslinking. 相似文献
55.
56.
The specification property for solenoidal automorphisms is discussed; a solenoidal automorphism satisfies specification iff is expansive, and satisfies weak specification but not specification iff is ergodic and central spin. These are problems set up byK. Sigmund for homeomorphisms with specification. The proofs for toral case are given byD. Lind. For solenoidal case, a key ingredient in our proofs is splitting theorems on solenoidal groups with respect to described in § 2. Moreover, the following is proved: (i) If obeys specification then satisfies weak specification and is densely periodic. But the converse is not necessarily true. (ii) Every solenoidal automorphism with specification admits a Markov partition. (iii) Every ergodic solenoidal automorphism without specification does not admit Markov partitions. (iv) There exists an expansive homeomorphism with specification which has not Markov partitions. 相似文献
57.
Biomimetic formation of gramicidin S by dimerization-cyclization of pentapeptide precursor on solid support 总被引:1,自引:0,他引:1
The biomimetic formation of gramicidin S, cyclo(-d-Phe-Pro-Val-Orn-Leu-)2, by the dimerization and cyclization of pentapeptide precursor without the protection of δ-amino group of the Orn residue was examined on a solid support. The cyclization of H-d-Phe-Pro-Val-Orn-Leu-oxime on a resin with an oxime group of 0.62 mmol/g in 1,4-dioxane directly gave gramicidin S in a 50% yield. The dimerization-cyclization mode on the solid support was similar to that of the biosynthesis of gramicidin S on an enzyme. 相似文献
58.
To evaluate the prognosis in 57 patients with old myocardial infarctions, 201Tl myocardial scintigraphy and 99mTc-HSA gated blood pool scan had been done as a 5-year follow up study. We subdivided into two groups; group I (over 60 years) and group II (under 60 years). Cardiac index (CI) and right ventricular ejection fraction (RVEF) did not change significantly, however left ventricular ejection fraction (LVEF) changed significantly (p less than 0.05). Correlationship between CAG score and delta LVEF by handgrip exercise test was y = -1.34 x +3.61 (n = 44, r = -0.400, p less than 0.01). Otherwise, Tl defect ratio between first and final examination did not show the significant change in two groups. In conclusion, nuclear examination (cardiac function and myocardial blood flow) is significant to evaluate the prognosis in patients with myocardial infarction. 相似文献
59.
Bunichiro Yamada Shinji Tagashira Shuzo Aoki 《Journal of polymer science. Part A, Polymer chemistry》1994,32(14):2745-2754
The dimerization of methyl methacrylate, ethyl methacrylate, methacrylonitrile, and α-methylstyrene to 2-substituted-1-allylic compounds [CH2?C(X)CH2C(CH3)2X] (X = COOR, C6H5, or CN), and methyl α-ethylacrylate to a 3-substituted-2-allylic compound [CH3CH?C(COOCH3)CH2C(CH3)(C2H5) COOCH3] was carried out by catalytic chain transfer using benzylbis (dimethylglyoximato) (pyridine) cobalt (III). These dimers were then used as addition-fragmentation chain transfer agents in the polymerizations of methyl methacrylate and styrene at 800C or above. Cross-dimers from methacrylic ester-α-methylstyrene and methacrylonitrile-α-methylstyrene mixtures were similarly prepared. Except for those from methyl α-ethylacrylate and methacrylonitrile, all the dimers participated in the addition-fragmentation and the copolymerization to different extents. The dimer of methyl α-ethylacrylate was actually inactive during the styrene and methyl methacrylate polymerizations. The methacrylonitrile dimer was primarily incorporated in the polymer chain through copolymerization. Among the dimer and the cross-dimers from α-methylstyrene with the other monomers, those bearing the α-methylstyrene moiety in the α-substituent [CH2?C(X)CH2C(CH3)2C6H5, X?COOCH3, COOC2H5, and CN] are noted as highly reactive chain transfer agents. © 1994 John Wiley & Sons, Inc. 相似文献
60.
Liquid-liquid extraction and spectrophotometric determination of palladium with 2-mercaptobenz-amide
2-Mercaptobenzamide (MBA) was investigated as a reagent for the extraction of palladium. The palladium complex of MBA was extracted into tributyl phosphate (TBP). The pKa of the ligand was 5.45 with the stability constant of the palladium complex β2=107.1. The composition of the complex in TBP was Pd:MBA:TBP=1:2:2. Addition of sodium chloride accelerated the rate of extraction. Various interfering ions could be masked with EDTA; Ag(I), Au(III), Os(VIII), Se(IV), Te(IV) etc. interfered. The molar absorptivity was 1.59×104 l mol?1 cm?1; 1–35 μg Pd could be determined at pH 6.0. 相似文献